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WO2004065669A1 - Composition pour element capacitif a film mince, film isolant a constante dielectrique elevee, element capacitif a film mince, condensateur lamine a films minces et procede de fabrication d'element capacitif a film mince - Google Patents

Composition pour element capacitif a film mince, film isolant a constante dielectrique elevee, element capacitif a film mince, condensateur lamine a films minces et procede de fabrication d'element capacitif a film mince Download PDF

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Publication number
WO2004065669A1
WO2004065669A1 PCT/JP2004/000273 JP2004000273W WO2004065669A1 WO 2004065669 A1 WO2004065669 A1 WO 2004065669A1 JP 2004000273 W JP2004000273 W JP 2004000273W WO 2004065669 A1 WO2004065669 A1 WO 2004065669A1
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Prior art keywords
thin film
film
composition
coating film
dielectric
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PCT/JP2004/000273
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English (en)
Japanese (ja)
Inventor
Yuki Miyamoto
Yukio Sakashita
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Tdk Corporation
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Filing date
Publication date
Application filed by Tdk Corporation filed Critical Tdk Corporation
Priority to US10/542,847 priority Critical patent/US20060279901A1/en
Priority to EP04702806A priority patent/EP1591567A1/fr
Priority to JP2005508042A priority patent/JP4529902B2/ja
Publication of WO2004065669A1 publication Critical patent/WO2004065669A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/10—Inorganic compounds or compositions
    • C30B29/16—Oxides
    • C30B29/22—Complex oxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G4/00—Fixed capacitors; Processes of their manufacture
    • H01G4/002—Details
    • H01G4/018—Dielectrics
    • H01G4/06—Solid dielectrics
    • H01G4/08—Inorganic dielectrics
    • H01G4/12—Ceramic dielectrics
    • H01G4/1209—Ceramic dielectrics characterised by the ceramic dielectric material
    • H01G4/1218—Ceramic dielectrics characterised by the ceramic dielectric material based on titanium oxides or titanates
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    • C01—INORGANIC CHEMISTRY
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    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/62605—Treating the starting powders individually or as mixtures
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    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/02—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of inorganic substances
    • H01B3/12—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of inorganic substances ceramics
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G4/00—Fixed capacitors; Processes of their manufacture
    • H01G4/30—Stacked capacitors
    • C—CHEMISTRY; METALLURGY
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    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
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    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
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    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/44—Metal salt constituents or additives chosen for the nature of the anions, e.g. hydrides or acetylacetonate
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    • C04B2235/658—Atmosphere during thermal treatment
    • C04B2235/6583—Oxygen containing atmosphere, e.g. with changing oxygen pressures
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Definitions

  • composition for thin film capacitor high dielectric constant insulating film, thin film capacitor, thin film multilayer capacitor, and method of manufacturing thin film capacitor
  • the present invention relates to a composition for a thin film capacitor, a high dielectric constant insulating film, a thin film capacitor, a thin film laminated capacitor, and a method for manufacturing a thin film capacitor.
  • thin-film capacitors using a single-layer dielectric thin film have been delayed in miniaturization of integrated circuits with active elements such as transistors, and have become a factor that hinders the realization of ultra-high integrated circuits.
  • the reason why the miniaturization of thin-film capacitors was delayed was that the dielectric constant of the dielectric material used was low. Therefore, it is important to use a dielectric material with a high dielectric constant in order to reduce the size of a thin film capacitor and achieve a high capacitance.
  • the dielectric constant may decrease as the dielectric film becomes thinner.
  • leak characteristics and breakdown voltage were sometimes deteriorated due to holes formed in the dielectric film due to thinning.
  • the formed dielectric film had poor surface smoothness, and the rate of change of the dielectric constant with temperature also tended to deteriorate.
  • high-capacitance capacitors that do not contain lead have been desired because of the impact of lead compounds such as PMN on the environment.
  • each dielectric layer in order to reduce the size and increase the capacity of the multilayer ceramic capacitor, the thickness of each dielectric layer must be as small as possible (thinning), and the dielectric layer in a given size must be reduced. It is desired to increase the number of stacked layers as much as possible (multilayering).
  • a dielectric green sheet layer is formed on a carrier film by a doctor method or the like using a sheet method (a paste for a dielectric layer), and the internal electrode layer paste is printed thereon in a predetermined pattern.
  • a sheet method a paste for a dielectric layer
  • the internal electrode layer paste is printed thereon in a predetermined pattern.
  • the multilayer ceramic capacitor is formed by a printing method (for example, a method of printing a plurality of pastes for dielectric layers and pastes for internal electrode layers on a carrier film alternately using a screen printing method and then peeling the carrier film). Manufacturing also has similar problems.
  • a printing method for example, a method of printing a plurality of pastes for dielectric layers and pastes for internal electrode layers on a carrier film alternately using a screen printing method and then peeling the carrier film. Manufacturing also has similar problems.
  • the dielectric thin films formed by the methods described in these publications have poor surface smoothness, and if they are laminated too much, the electrodes may be short-circuited. As a result, the number of laminated layers is at most about 12 to 13 layers. Only things could be manufactured. For this reason, even if the capacitor could be miniaturized, high capacity could not be achieved.
  • composition formula is represented by: (B i 2 + 2 ) 2+ (A m- ! B m 0 3m + 1 ) 2 _ or B i 2 Am _!
  • Symbol m is a positive number from 1 to 8
  • symbol A is at least one element selected from Na, K, Pb, Ba, Sr, Ca and Bi
  • symbol B is Fe, Co, Cr , Ga, Ti, Nb, Ta, Sb, V, Mo, and at least one element selected from the group consisting of the bismuth layered compound dielectric of palc obtained by the sintering method itself.
  • the composition represented by the above composition formula was formed into a thin film (eg, 1 ⁇ or less) under any conditions (eg, the relationship between the substrate surface and the degree of c-axis orientation of the compound). Even if it is thin, it can provide a relatively high dielectric constant and low loss even if it is thin, and obtain a thin film with excellent leakage characteristics, improved withstand voltage, excellent temperature characteristics of dielectric constant, and excellent surface smoothness. None was disclosed about what could be done. [0015]
  • the present inventors have developed a composition for a thin film capacitor shown in PCT / JP 02/08574 below, and have filed an application first.
  • the present inventors have found that by including Bi in excess of the stoichiometric composition of the bismuth layered compound, the degree of c-axis orientation of the compound can be further improved.
  • the present invention has been completed.
  • the thin film composed of the composition for a thin film capacitor shown in PCT / JP 02/08574 can be formed by various thin film forming methods such as a CVD method, an evaporation method, and a sputtering method.
  • a CVD method a chemical vapor deposition method
  • evaporation method a physical vapor deposition method
  • sputtering method a physical vapor deposition method
  • the present invention has been made in view of such circumstances, and its object is to provide a composition for a thin film capacitor, which has a high degree of c-axis orientation and particularly excellent leak current resistance, a high dielectric constant insulating film, a thin film capacitor,
  • An object of the present invention is to provide a method for manufacturing a thin film multilayer capacitor and a thin film capacitor.
  • Another object of the present invention is to produce a thin film capacitor having a high degree of c-axis orientation and excellent in leakage current resistance, particularly by forming by a solution method. [0 0 1 9]
  • the present inventors have conducted intensive studies on the material and the crystal structure of the dielectric thin film used for the capacitor. As a result, the present inventors have found that a bismuth layered compound having a specific composition is used, and that the c-axis ([0 0 1] Orientation) perpendicular to the substrate surface to form a dielectric thin film as a composition for a thin film capacitor, that is, a c-axis oriented film of a bismuth layered compound with respect to the substrate surface.
  • a thin film normal parallel (parallel to the c-axis)
  • a relatively high dielectric constant and low loss low tan S
  • compositions for a thin film capacitor having excellent temperature characteristics of dielectric constant and excellent surface smoothness and a thin film capacitor using the same can be provided.
  • the present inventors have also found that the use of such a composition for a thin film capacitor as a dielectric thin film enables the number of layers to be increased, and to provide a thin film multilayer capacitor which is small and can provide a relatively high capacitance. It was completed. Furthermore, they have found that by using such a composition as a high-dielectric-constant insulating film, it can be applied to uses other than thin-film capacitive elements, and have completed the present invention.
  • the present inventors have determined that the Bi content of the bismuth layered compound is excessively contained in the composition at a predetermined excess content with respect to the stoichiometric composition of the bismuth layered compound, whereby the degree of c-axis orientation is obtained. Have been found to be able to improve the leakage current resistance as well as to improve the present invention, and have completed the present invention.
  • composition for a thin film capacitor according to the first aspect of the present invention comprises:
  • a bismuth layered compound in which the c-axis is oriented perpendicular to the substrate surface has the composition formula: (B i 2 0 2 ) 2+ (A m -B m 0 3m + i) 2 or B i 2 A m -i B m 0 3ni + 3 , wherein the symbol m in the composition formula is an odd number, and the symbol A is at least one selected from Na , K, Pb, Ba, Sr, Ca and Bi .
  • the symbol B is at least one element selected from Fe, Co, Cr, Ga, Ti, Nb, Ta, Sb, V, Mo and W;
  • B i of the bismuth layer compound the composition formula: (B i 2 0 2) 2+ (AB m 0 3m + i) 2 — or B i 2 A m- ! B m 0 3m + 3 is contained in excess, and the excess content of B i is 0 It is characterized in that it is in the range of 0.6 ⁇ mole.
  • the excess content of Bi is, in terms of Bi, 0.1.l ⁇ B i ⁇ 0.6 Xmole, and more preferably 0.4.ltoreq.B i.
  • the range is 0.6 Xmole, particularly preferably 0.4 ⁇ Bi ⁇ 0.5 Xmole.
  • m in the composition formula constituting the bismuth layered compound is preferably any one of 1, 3, 5, 7 and more preferably any one of 1, 3, 5 It is. This is because manufacturing is easy.
  • composition for a thin film capacitor according to the second aspect of the present invention is the composition for a thin film capacitor according to the second aspect of the present invention.
  • a bismuth layered compound in which the c-axis is oriented perpendicular to the substrate surface is represented by a composition formula: B i 4 T ia 0 12 ,
  • B i of the bismuth layer compound the composition formula: with respect to B i 4 T ia 0 12, Yes is excessively added, an excess amount of the B i is in B i terms, 0 rather B i rather It is characterized by a range of 1.8 moles.
  • composition for a thin film capacitor according to the third aspect of the present invention is the composition for a thin film capacitor according to the third aspect of the present invention.
  • a bismuth layered compound in which the c-axis is oriented perpendicular to the substrate surface is represented by a composition formula: B i 4 + disturbT ia 0 12 ,
  • the bismuth layered compound is characterized in that the number of moles of excess Bi is 0 and ct ⁇ 1.8.
  • ⁇ which is the molar number of excess Bi in the bismuth layered compound, is 0.1 l ⁇ a ⁇ 1.8, more preferably 0.4 ⁇ ⁇ ⁇ 1.8. Particularly preferably, it is in the range of 0.4 ⁇ ⁇ ⁇ 1.5.
  • the term “thin film” as used in the present invention means a film of a material having a thickness of several A to several meters formed by various thin film forming methods, and a thick film of several hundreds m or more formed by a sintering method. The purpose is to exclude balta.
  • the thin film includes not only a continuous film that continuously covers a predetermined region, but also an intermittent film that intermittently covers an arbitrary interval.
  • the thin film may be formed on a part of the substrate surface, or may be formed on the entire surface.
  • rare earth elements Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and At least one element selected from Lu.
  • the leak characteristics can be further improved.
  • the c-axis of the bismuth layered compound is oriented at 100% perpendicular to the substrate surface, that is, the degree of c-axis orientation of the bismuth layered compound is 100%, but it is not necessary that The degree of axial orientation need not be 100%.
  • the degree of c-axis orientation of the bismuth layered compound is 80% or more, more preferably 90% or more, and particularly preferably 95% or more.
  • the operational effects of the present invention are improved.
  • the composition for a thin film capacitor according to the present invention has a relatively high dielectric constant (for example, more than 100) and low loss (ta ⁇ ⁇ is 0.02 or less), and has excellent leak resistance (for example, electric field strength of 50 kVZcm). in the measured leakage current is 5 X 1 0- 7 A / cm 2 or less), the breakdown voltage is improved (e.g. 1 000 k V / cm or higher).
  • composition for a thin film capacitor according to the present invention can provide a relatively high dielectric constant even when thin, and has good surface smoothness. It is also possible to increase the number of thin films stacked. Therefore, like this By using a composition for a thin film capacitor, it is possible to provide a thin film laminated capacitor which is small and can provide a relatively high capacity.
  • composition for a thin film capacitor and the thin film capacitor of the present invention are excellent in frequency characteristics (for example, the value of the dielectric constant at a high frequency region of 1 MHz at a specific temperature and the value of 1 kHz at a lower frequency region thereof).
  • excellent in voltage characteristics (absolute ratio of 0.9 to 1.1) with respect to the dielectric constant at z for example, the dielectric constant at a measurement voltage of 0.1 V at a specific frequency and the The ratio of the dielectric constant at a voltage of 5 V to the absolute value is 0.9 to 1.1).
  • the composition for a thin film capacitor of the present invention has excellent capacitance temperature characteristics (the average change rate of the capacitance with respect to temperature in a temperature range of ⁇ 55 ° C. to + 150 ° C.) , At a reference temperature of 25 ° C, within ⁇ 500 ppm / ° C).
  • the thin film capacitor examples include, but are not limited to, a capacitor having a conductor-insulator-conductor structure (for example, a single-layer thin-film capacitor, a multilayer-type thin-film multilayer capacitor, etc.) and a capacitor (for, for example, a DRAM). And the like.
  • a capacitor having a conductor-insulator-conductor structure for example, a single-layer thin-film capacitor, a multilayer-type thin-film multilayer capacitor, etc.
  • a capacitor for, for example, a DRAM.
  • the composition for a thin film capacitor is not particularly limited, and examples thereof include a dielectric thin film composition for a capacitor and a dielectric thin film composition for a capacitor.
  • the high dielectric constant insulating film according to the present invention is composed of the same composition as the composition for a thin film capacitor according to the present invention.
  • the high dielectric constant insulating film of the present invention can be used, for example, as a gate insulating film of a semiconductor device, an intermediate insulating film between a gate electrode and a floating gate, etc., in addition to a thin film dielectric film of a thin film capacitor or a capacitor. Can be used.
  • a thin film capacitor in which a lower electrode, a dielectric thin film and an upper electrode are sequentially formed on a substrate,
  • the dielectric thin film comprising the composition for a thin film capacitor according to any of the above is there.
  • the thickness of the dielectric thin film is from 1 to 100 nm, more preferably from 10 to 500 nm. In the case of such a thickness, the operation and effect of the present invention are large.
  • a thin film laminated capacitor in which a plurality of dielectric thin films and internal electrode thin films are alternately laminated on a substrate,
  • the dielectric thin film is made of the composition for a thin film capacitor described in any of the above.
  • the thickness of the dielectric thin film is from 1 to 100 nm, more preferably from 10 to 500 nm. In the case of such a thickness, the operation and effect of the present invention are large.
  • the bismuth layered compound is composed of the composition for a thin film capacitor described in any of the above.
  • the method for manufacturing a thin film capacitor according to the present invention includes:
  • the coating film is dried, and thereafter, the coating film is calcined at a temperature at which the coating film does not crystallize. After that, the coating film is baked.
  • the coating film is dried, another coating film is formed on the dried coating film, and the process of drying the coating film is repeated to obtain a coating film having a desired film thickness. Then, the applied film is fired. In this case, after the application and the drying are repeated one or more times, it may be calcined and then calcined.
  • the step of drying and calcining the coating film, forming another coating film on the calcined coating film, and drying and calcining the coating film is repeated.
  • a coating film having a desired thickness is obtained, and thereafter, the coating film is fired.
  • the drying may be omitted, and the coating and calcination may be repeated, followed by baking.
  • the process of drying the coating film, pre-baking, and then baking is repeated to obtain a dielectric thin film having a desired film thickness.
  • drying may be omitted, and application, calcination, and firing may be repeated.
  • calcination may be omitted, and application, drying, and firing may be repeated.
  • the temperature at which the coating film is fired is 600 to 900 ° C., which is the crystallization temperature of the coating film.
  • the temperature at which the coating film is dried is room temperature (25 ° C.) to 400 ° C.
  • the temperature at which the coating film is calcined is 200 to 700 ° C. [0 0 5 2]
  • the film thickness of the unbaked coating film before baking is applied, dried and dried so that the film thickness after baking is 200 nm or less, preferably 10 to 200 nm.
  • the film thickness after baking is 200 nm or less, preferably 10 to 200 nm.
  • Repeat hopping and / or calcining If the thickness of the coating film before firing is too thick, after firing, It tends to be difficult to obtain a well-crystallized c-axis oriented bismuth layered compound film. On the other hand, if it is too thin, the firing must be repeated many times in order to obtain a dielectric thin film having a desired thickness, which is not economical.
  • the temperature at the time of the heat treatment is preferably from 400 to 100 ° C.
  • FIG. 1A and 1B are schematic cross-sectional views showing a manufacturing process of a thin film capacitor according to one embodiment of the present invention.
  • FIG. 2 is a flowchart showing a manufacturing process of the thin film capacitor shown in FIG. 1
  • FIG. 3 is a schematic sectional view of a thin film multilayer capacitor according to another embodiment of the present invention
  • FIG. FIG. 4 is a graph showing the relationship between the excess content of Bi in the dielectric thin film, the firing temperature, and the degree of orientation;
  • FIG. 5 is a graph showing frequency characteristics of the dielectric thin film of the thin film capacitor according to the embodiment of the present invention.
  • FIG. 6 is a graph showing a voltage characteristic of the dielectric thin film of the thin film capacitor according to the example of the present invention.
  • a thin film capacitor in which a dielectric thin film is formed as a single layer is used as a thin film capacitor.
  • a description will be given using a densa as an example.
  • a thin film capacitor 2 As shown in FIG. 1, a thin film capacitor 2 according to one embodiment of the present invention has a substrate 4, on which a lower electrode thin film 6 is formed via an insulating layer 5. On the lower electrode thin film 6, a dielectric thin film 8 is formed. An upper electrode thin film 10 is formed on the dielectric thin film 8.
  • the substrate 4 is not particularly limited, lattice-match well monocrystal (e.g., S r T I_ ⁇ 3 single crystal, MgO single crystal, such as L aA 10 3 single crystal), an amorphous material (e.g., glass, fused quartz, etc. S i 0 2 ZS i), for example other materials (for, Z r 0 2 / / S i, consists Ce_ ⁇ 2 / S i, etc.) and the like.
  • the thickness of the substrate 4 is not particularly limited, and is, for example, about 100 to 1,000.
  • a silicon single crystal substrate is used as the substrate 4, and an insulating layer 5 having a thermal oxide film (silicon oxide film) is formed on the surface thereof, and a lower electrode thin film 6 is formed on the surface thereof. It is formed.
  • the c-axis-oriented dielectric film can be extremely easily formed using not only a lower electrode oriented in the [100] direction but also an amorphous, non-oriented, and an electrode oriented in a direction other than the [100] direction. Can be manufactured.
  • the lower electrode film 6 when the substrate 4 using the lattice-match well monocrystal For example other, conductive oxides such as CaRu_ ⁇ 3 and S RRu_ ⁇ 3, or composed of a noble metal such as P t and Ru It is preferably made of a conductive oxide or a noble metal oriented in the [100] direction.
  • a conductive oxide or a noble metal oriented in the [100] direction can be formed on the surface thereof.
  • Such a lower electrode thin film 6 is produced by a normal thin film forming method.
  • the lower electrode thin film 6 is formed by a physical vapor deposition method such as a sputtering method or a pulse laser vapor deposition method (PLD).
  • PLD pulse laser vapor deposition method
  • Substrate 4 temperature preferably 300 ° C or more, More preferably, the temperature is preferably set to 500 ° C. or higher.
  • the lower electrode thin film 6 may be, for example,
  • conductive glass such as 1TO.
  • the substrate 4 When a single crystal having good lattice matching is used for the substrate 4, it is easy to form the lower electrode thin film 6 oriented in the [100] direction on the surface thereof, thereby forming the lower electrode thin film 6 on the lower electrode thin film 6.
  • the c-axis orientation of the resulting dielectric thin film 8 tends to increase.
  • an amorphous material such as glass is used for the substrate 4
  • lower electrode thin films 6 include, for example, noble metals such as gold (Au), palladium (Pd), and silver (Ag) or alloys thereof, and base metals such as nickel (N i) and copper (Cu). Those alloys can be used.
  • noble metals such as gold (Au), palladium (Pd), and silver (Ag) or alloys thereof
  • base metals such as nickel (N i) and copper (Cu). Those alloys can be used.
  • the thickness of the lower electrode thin film 6 is not particularly limited, but is preferably 10 to 1000 nm, and more preferably about 50 to 200 nm.
  • the upper electrode thin film 10 can be made of the same material as the lower electrode thin film 6.
  • the thickness may be the same.
  • the dielectric thin film 8 is composed of the composition for a thin film capacitor of the present invention, and has a composition formula: (B i 0 2 ) 2+ (A m ⁇ ! B m 0 3m + i) 2_ , or B i A m ⁇ containing i B m 0 bismuth layer compound expressed by 3m + 3.
  • a bismuth layer compound the (m-1) pieces of AB0 layered structure of upper and lower laminar base Robusukai coat layer with continuous constitute Bae Robusukai preparative grating, is sandwiched with a layer of the pair of B i and O 3 Show.
  • the symbol m is not particularly limited as long as it is an odd number. If the symbol m is an odd number, it has a polarization axis also in the c-axis direction, and the dielectric constant at the Curie point is higher than when the symbol m is an even number. The temperature characteristic of the permittivity tends to deteriorate when m is an even number. It shows better characteristics than conventional BST. In particular, increasing the symbol m can be expected to further increase the dielectric constant.
  • the symbol A is composed of at least one element selected from Na, K, Pb, Ba, Sr, Ca and Bi.
  • the symbol A is composed of two or more elements, their ratio is arbitrary.
  • the symbol B is composed of at least one element selected from Fe, Co, Cr, Ga, Ti, Nb, Ta, Sb, V, Mo and W.
  • the symbol B is composed of two or more elements, their ratio is arbitrary.
  • B i of the bismuth layer compound the composition formula:! (B i 2 0 2 ) 2+ (AB m 0 3m + i) 2 one or B i z A m, - B m 0 3m + 3
  • the excess content of Bi is in the range of 0 to Bi to 0.6 Xmole in terms of Bi.
  • the excess content of B i is 0.1 ⁇ B i ⁇ 0.6 Xmole, more preferably 0.4 ⁇ B i ⁇ 0.6 Xm, in terms of Bi, particularly preferred. Is in the range 0.4 ⁇ B i ⁇ 0.5 X mmol.
  • ⁇ is bismuth layer compound is a 3 formula: in the case of B i 4 T i 0 12 bismuth layer compound expressed by an excess amount of B i is a B i terms, 0 It is in the range of 1.8 (0.6 X 3 (m)) moles.
  • this bismuth layered compound is represented by the composition formula: Bi 4+ «T i 0 12 , ⁇ , which is the molar number of excess Bi contained in the bismuth layered compound, is 0 and ⁇ ⁇ 1.8. , Preferably 0.4 ⁇ ⁇ : ⁇ 1.8, more preferably 0.4 ⁇ ⁇ ⁇ 1.5.
  • the orientation of the bismuth layered compound in the [001] direction that is, the c-axis
  • the dielectric thin film 8 is formed such that the c-axis of the bismuth layered compound is oriented perpendicular to the white plate 4.
  • the c-axis orientation of the bismuth layered compound is 100 ° / 0 , but the c-axis orientation is not necessarily 100%, and preferably 80% of the bismuth layered compound.
  • the above, more preferably 90% or more, and even more preferably 95% or more should be c-axis oriented.
  • the c-axis orientation degree of the bismuth layered compound is preferably 80% or more.
  • the bismuth layered compound is c-axis oriented using various thin film forming methods described below, the bismuth layered compound preferably has a c-axis orientation of 90% or more, more preferably 95% or more. Les ,.
  • the degree of c-axis orientation (F) of the bismuth layered compound here is defined as P 0, which is the c-axis diffraction intensity ratio of a polycrystal having completely random orientation, and P c is the actual c-axis diffraction intensity ratio.
  • F (%) (PP 0) / (1-P 0) XI 00 ... is obtained by (Equation 1).
  • P in Equation 1 is the sum of the total reflection intensity I (00 1) of the reflection intensity I (00 1) from the (00 1) plane and the reflection intensity I (hk l) from each crystal plane (hk 1). ⁇ I (hk 1) ( ⁇ I (00 1) / ⁇ I (hk 1) ⁇ ), and the same applies to P 0.
  • Equation 1 the X-ray diffraction intensity P when the crystal is oriented 100% in the c-axis direction is 1.
  • F 0 ° / o
  • the c-axis of the bismuth layer compound the pair (B i 2 0 2) 2+ layer direction connecting to each other, i.e., means [001] orientation.
  • the dielectric properties of the dielectric thin film 8 are maximized. That is, the dielectric thin film 8 has relatively high dielectric constant and low loss (low ta ⁇ ⁇ ), excellent leakage resistance, improved withstand voltage, excellent dielectric constant temperature characteristics, and surface smoothness. Excellent in nature You. If tan ⁇ decreases, the loss Q (1 / ta ⁇ ⁇ ) value increases.
  • the dielectric thin film 8 Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, It is preferable to further have at least one element selected from Yb and Lu (rare earth element Re).
  • Amount substitution by rare earth elements, for varies depending on the value of Paiiota, was example, if m 3, the stoichiometric compositional formula: B i A 2 - in the x Re x B 3 0 12, preferably 0. 4 ⁇ X ⁇ l. 8, more preferably 1.0 ⁇ 1.4.
  • the dielectric thin film 8 does not have the rare-earth element Re, it has excellent leakage characteristics as described later, but the leakage characteristics can be further improved by Re substitution.
  • the dielectric thin film 8 does not have a rare earth element R e, a leakage current measured at the electric field intensity 5 O k VZ cm, preferably 5 X 10- 7 A / cm 2 or less, more preferably 5 X 10 can be a single 8 a / cm 2 or less.
  • the dielectric thin film 8 has a rare earth element Re, the leakage current when measured under the same conditions, preferably 5 X 10- 8 A / cm 2 or less, more preferably 1 X 10 one 8 AZcm 2 or less.
  • the dielectric thin film 8 preferably has a thickness of 1 to 1000 nm, and more preferably 1 to 500 or less from the viewpoint of increasing the capacity.
  • the dielectric constant of the dielectric thin film 8 at 25 ° C. (room temperature) and a measurement frequency of 100 kHz (AC 20 mV) is preferably more than 100, more preferably 120 or more.
  • the tan ⁇ force at 25 ° C. (room temperature) and a measurement frequency of 100 kHz (AC 20 mV) is preferably 0.02 or less, more preferably 0.01 or less. Further, the loss Q value is preferably 50 or more, more preferably 100 or more.
  • the dielectric thin film 8 even if the frequency at a specific temperature (for example, 25 ° C.) is changed to a high frequency region of, for example, about 1 MHz, a change (particularly, a decrease) in the dielectric constant is small.
  • the absolute value of the ratio between the value of the dielectric constant at 1 MHz in the high-frequency region at a specific temperature and the value of the dielectric constant at 1 kHz in the lower-frequency region is 0. 9 to 1.1. That is, the frequency characteristics are good.
  • the change in the dielectric constant is small.
  • the absolute value of the ratio between the value of the dielectric constant at a measurement voltage of 0.9 V at a specific frequency and the value of the dielectric constant at a measurement voltage of 5 V is 0.9 to 1.1. can do. That is, the voltage characteristics are good.
  • Such a dielectric thin film 8 is formed by various thin film forming methods such as a vacuum evaporation method, a high-frequency sputtering method, a pulse laser deposition method (PLD), a MOC VD (Metal Organic Chemical Vapor Deposition) method, and a sol-gel method. Can be formed.
  • various thin film forming methods such as a vacuum evaporation method, a high-frequency sputtering method, a pulse laser deposition method (PLD), a MOC VD (Metal Organic Chemical Vapor Deposition) method, and a sol-gel method.
  • PLD pulse laser deposition method
  • MOC VD Metal Organic Chemical Vapor Deposition
  • this dielectric thin film 8 can be particularly manufactured by the following method.
  • a raw material solution for forming the dielectric thin film 8 shown in FIG. 1 is prepared.
  • the dielectric thin film 8 for example, the composition formula: When represented by B i 4 + ⁇ T i 3 0 12 has a hexanoic acid solution to 2 Echiru of hexanoic acid B i to 2 Echiru, the 2- Echiru Prepare a toluene solution of Ti xanic acid.
  • this raw material solution is applied on the lower electrode 6 shown in FIG.
  • the coating method is not particularly limited, and a method such as spin coating, dip coating, spraying, or painting with a brush can be used.
  • a coating film of, for example, about 5 to 600 nm can be formed.
  • this coating film is dried in air to evaporate the solvent in the coating film.
  • the drying temperature is from room temperature to about 400 ° C.
  • the dried coating film is calcined (not crystallized) in an oxygen atmosphere.
  • the calcining temperature is about 200 to 700 ° C.
  • the steps from application to calcination are repeated at least once on the applied film after calcination. If the thickness of the unfired coating film before firing is too large, it tends to be difficult to obtain a c-axis oriented bismuth layered compound film that is well crystallized after firing.
  • the applied film is subjected to main firing (also simply referred to as “firing”).
  • the temperature at the time of the main baking is performed under a temperature condition at which the coating film is crystallized, and the temperature is preferably 400 to 100 ° C.
  • the atmosphere during the main firing is not particularly limited, but is an oxygen gas atmosphere.
  • the main baking after the repetition of coating and calcination is repeated one or more times to obtain a dielectric thin film 8 having a final film thickness of about 1 to 100 nm.
  • the thickness of the unbaked coating film after one baking is 200 nm or less, preferably 10 to 200 nm after one baking. It is preferable to set as follows. If the thickness of the coating film before baking is too large, it tends to be difficult to obtain a well-crystallized c-axis oriented bismuth layered compound film after baking. Also, If it is too thin, the main firing must be repeated many times in order to obtain a dielectric thin film having a desired thickness, which is not economical.
  • the dielectric thin film 8 thus obtained is composed of a bismuth layered compound containing excessive bismuth, and its c-axis is oriented perpendicular to the substrate 4.
  • the degree of c-axis orientation of the bismuth layered compound is preferably at least 80%, more preferably at least 90%, further preferably at least 95%.
  • the heat treatment is preferably performed at a temperature of 400 to 100 ° C.
  • Such a dielectric thin film 8 and a thin film capacitor 2 using the same have a relatively high dielectric constant and low loss, excellent leakage characteristics, improved withstand voltage, excellent dielectric constant temperature characteristics, and excellent surface characteristics. Excellent in smoothness.
  • Such a dielectric thin film 8 and a thin film capacitor 2 have excellent frequency characteristics and voltage characteristics.
  • a thin film multilayer capacitor in which a dielectric thin film is formed in multiple layers will be described as an example of a thin film capacitor.
  • the thin-film multilayer capacitor 20 has a capacitor body 22.
  • the capacitor element 22 has a plurality of dielectric thin films 8a and a plurality of internal electrode thin films 24 and 26 alternately arranged on a substrate 4a, and furthermore, a dielectric thin film 8a arranged at the outermost side. It has a multilayer structure in which a protective layer 30 is formed so as to cover the surface.
  • a pair of external electrodes 28, 29 are formed at both ends of the capacitor body 22, and the pair of external electrodes 28, 29 are alternately formed in the capacitor body 22.
  • the capacitor circuit is electrically connected to the exposed end faces of the disposed internal electrode thin films 24, 26. Configure the road.
  • the shape of the capacitor body 22 is not particularly limited, but is usually a rectangular parallelepiped.
  • the dimensions are not particularly limited, but are, for example, about vertical (0.01 to 1 Omm) X horizontal (0.01 to 1 Omm) X height (0.01 to 1 mm).
  • the substrate 4a is made of the same material as the substrate 4 of the first embodiment described above.
  • the dielectric thin film 8a is made of the same material as the dielectric thin film 8 of the first embodiment described above.
  • the internal electrode thin films 24 and 26 are made of the same material as the lower electrode thin film 6 and the upper electrode thin film 10 of the first embodiment described above.
  • the thickness is not particularly limited, but may be, for example, about 10 to 100 nm.
  • the material of the protective layer 30 is not particularly limited, and is made of, for example, a silicon oxide film, an aluminum oxide film, or the like.
  • the thin-film multilayer capacitor 20 is formed by forming a first-layer internal electrode thin film 24 on a substrate 4 a by applying a mask such as a metal mask, and then forming a dielectric thin film 8 a on the internal electrode thin film 24. Then, a second-layer internal electrode thin film 26 is formed on the dielectric thin film 8a. After repeating such a process a plurality of times, the outermost dielectric thin film 8a opposite to the substrate 4a is covered with the protective film 30, so that the internal electrode thin film 24, A capacitor element body 22 is formed in which a plurality of 26 and dielectric thin films 8 are alternately arranged. By covering with the protective film 30, the effect of moisture in the air on the inside of the capacitor body 22 can be reduced.
  • the odd-numbered internal electrode thin film 24 is electrically connected to the negative external electrode 28. Conduction occurs, and the even-numbered internal electrode thin film 26 is electrically connected to the other external electrode 29 to conduct, and the thin film multilayer capacitor 20 is obtained.
  • the substrate 4a made of an amorphous material.
  • the dielectric thin film 8a used in the present embodiment has a relatively high dielectric constant even if it is thin and has good surface smoothness. Therefore, the number of stacked layers should be 20 or more, preferably 50 or more. It is possible. For this reason, it is possible to provide the thin film laminated capacitor 20 which is small and can provide a relatively high capacity.
  • the average change rate of the dielectric constant with respect to the temperature in at least the temperature range of ⁇ 55 ° C. to + 150 ° C. ( ⁇ ) i ⁇ 500 It is preferably within a range of p pm / ⁇ C (reference temperature 25 ° C), and more preferably within a range of ⁇ 300 ppm / ° C.
  • the dielectric thin film 8 is represented by a stoichiometric composition formula B i 4 T i 3 O i 2 (B i T), and the composition formula: B i 2 A m -i B m 0 3m + 3
  • a 2-ethylhexanoic acid solution of 2-ethylhexanoic acid B i and a toluene solution of 2-ethylhexanoic acid T i were prepared as raw material solutions. That is, compared to the case of mixing 2-biethylenohexanoic acid B i at a stoichiometric ratio, such as (4 + o monole and 2-ethylinohexaenoic acid Ti at 3 monoles), These two solutions were mixed and diluted with toluene so that the molar amount of the raw materials was increased to obtain a raw material solution. [0 1 0 6]
  • Each of these raw material solutions was filtered in a clean booth using a 0.2 / im PTFE syringe filter in a clean room in a clean room.
  • a substrate 4 for forming a dielectric thin film 8 was prepared.
  • the substrate 4 was a silicon single crystal (100) substrate, and an insulating layer 5 as a silicon oxide film was formed on the surface of the substrate 4 by a thermal oxidation process.
  • the thickness of the insulating layer 5 was 0.5 ⁇ m.
  • a lower electrode 6 made of a Pt thin film was formed to a thickness of 0.1 ⁇ by a sputtering method.
  • the area of the substrate 4 was 5 mra ⁇ 1 Omm.
  • This substrate 4 is prepared in the number of types of raw material solutions, each is set on a spin coater, and about 10 ⁇ L of each raw material solution is added to the surface of the lower electrode 6 on the substrate 4 to obtain 400 ⁇ l.
  • Spin coating was performed under the conditions of rpm and 20 seconds to form a coating film on the surface of the lower electrode 6.
  • the substrate 4 was put in a thermostat (air inside) set at 150 ° C. and dried for 10 minutes. After 10 minutes, the substrate 4 is taken out, and as shown in FIG. 1A, a part of the coating film for forming the dielectric thin film 8 is wiped off so as to expose a part of the surface of the lower electrode 6.
  • a thermostat air inside
  • each substrate 4 was placed in an annular furnace in order to calcine the coating film.
  • oxygen was flowed at 0.3 liter / minute, the temperature was raised to 400 ° C. at a heating rate of 10 ° KZ, and after holding at 400 ° C. for 10 minutes. , Cooling rate 10 °
  • the temperature was reduced in KZ minutes. Calcination is performed at a temperature that does not crystallize the coating film. ⁇
  • each substrate was placed in an annular furnace in order to fully bake the calcined film.
  • oxygen is flowing at 5 milliliter / minute
  • the temperature is raised to 850 ° C at a heating rate of 80 ° C / minute, and after holding at 850 ° C for 30 minutes, the cooling rate is 80 ° C.
  • the temperature was lowered at a rate of 1 minute, and a part of the dielectric thin film 8 was obtained.
  • the thickness of a part of the dielectric thin film 8 after the main baking was about 80 nm.
  • each dielectric thin film 8 was measured by X-ray diffraction (XRD), it was found to be oriented in the [00,1] direction, that is, c-axis orientation perpendicular to the surface of the silicon single crystal substrate 4. I was able to confirm that.
  • the c-axis orientation degree F (%) was determined for each dielectric thin film.
  • the c-axis orientation degree (%) was determined by applying the Lottgering method in the range of 10 to 35 degrees according to the measured XRD pattern. The results are shown in Table 1 and FIG.
  • the surface roughness (Ra) of each dielectric thin film 8 was measured with an AF (atomic force microscope, manufactured by Seiko Instruments Inc., SPI 3800) according to JIS-B0601. Table 1 shows the results.
  • each dielectric thin film 8 has a?
  • the upper electrode 10 made of 1 was formed by a sputtering method, and samples of a plurality of types of thin film capacitors were produced. [0116]
  • the temperature characteristics of the electrical characteristics (dielectric constant, 1: & 3, loss (three values, leak current, short-circuiting ratio)) and dielectric constant of the obtained capacitor sample were evaluated.
  • Dielectric constant (no unit) was measured at room temperature (25 ° C) and measurement frequency of 100 kHz using an impedance analyzer (HP4194A) for the capacitor sample.
  • Leak current characteristics (unit: AZcin 2 ) were measured at an electric field strength of 50 kVZ cm.
  • the temperature characteristics of the dielectric constant are as follows: When the dielectric constant is measured for the capacitor sample under the above conditions and the reference temperature is 25 ° C, the dielectric constant with respect to the temperature within the temperature range of ⁇ 55 to + 150 ° C The average rate of change ( ⁇ ) was measured, and the temperature coefficient (ppm / ° C) was calculated. Table 1 shows the results.
  • ⁇ indicating the excess content of Bi is in the range of 0 to 1.8, preferably 0.1 ⁇ ⁇ 1.8, and more preferably 0.4 ⁇ 1.8 In a particularly preferred range of 0.4 ⁇ 1.5, the degree of c-axis orientation is improved and -It was confirmed that the leakage current was small and the leakage resistance was excellent.
  • the excess content of Bi i ⁇ 0.6 X mmol, preferably 0.l ⁇ B i ⁇ 0.6 X mmol, more preferably 0.4 B i ⁇ 0.6, especially preferably 0.4 ⁇ B In the range of i ⁇ 0.5 X mmol, it can be expected that the c-axis orientation degree is improved, the leak current is small, and the leak resistance is excellent.
  • a capacitor sample having a dielectric thin film 8 was prepared in the same manner as in Example 1 except that the holding temperature during the main firing was changed in the range of 600 ° C to 900 ° C, and the same as in Example 1 was performed. The test was performed. The results are shown in Table 2 and FIG.
  • the frequency characteristics were evaluated as follows. For the capacitor sample, the frequency was changed from 1 kHz to l] vtHz at room temperature (25 C), the capacitance was measured, and the permittivity was calculated. Figure 5 shows the results. An impedance analyzer was used to measure the capacitance. As shown in Fig. 5, it was confirmed that the value of the dielectric constant did not change even if the frequency at a specific temperature was changed to 1 MHz. That is, it was confirmed that the frequency characteristics were excellent.
  • the voltage characteristics were evaluated as follows. For the capacitor sample, the measured voltage (applied voltage) at a specific frequency (100 kHz) was changed from 0.4 (electric field strength 5 kV / cm) to 5 V (electric field strength 250 kV / cm) and the specific voltage was changed.
  • Figure 6 shows the results of measuring the capacitance below (measuring temperature 25 ° C) and calculating the permittivity. An impedance analyzer was used for measuring the capacitance. As shown in Fig. 6, it was confirmed that the value of the dielectric constant did not change even when the measurement voltage at a specific frequency was changed to 5 V. That is, it was confirmed that the voltage characteristics were excellent.
  • a composition for a thin film capacitor having a high degree of c-axis orientation and particularly excellent in leak current resistance, a high dielectric constant insulating film, a thin film capacitor, a thin film multilayer capacitor, and a thin film A method for manufacturing a capacitor can be provided.
  • a thin film capacitor having a dielectric thin film having a high degree of c-axis orientation and having excellent leakage current resistance can be easily manufactured by forming the film by a solution method.

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Abstract

La présente invention a trait à une composition pour un élément capacitif à film mince dans laquelle une couche de bismuth présentant son axe c orienté perpendiculaire à la surface d'un substrat est représentée par la formule empirique suivante : (Bi2O2)2+(Am-1BmO3m+1)2- ou Bi2Am-1BmO3m+3, dans laquelle : m est un nombre impair ; A représente au moins un élément choisi par Na, K, Pb, Ba, Sr, Ca et Bi ; et B représente au moins un élément choisi parmi Fe, Co, Cr, Ga, Ti, Nb, Ta, Sb, V, Mo et W, caractérisée en ce que ladite couche de bismuth contient du Bi en excès de ladite formule empirique : (Bi2O2)2+(Am-1BmO3m+1)2- ou Bi2Am-1BmO3m+3 et la quantité excédentaire de Bi est comprise entre 0 < Bi < 0,6X m moles en termes de Bi.
PCT/JP2004/000273 2003-01-21 2004-01-16 Composition pour element capacitif a film mince, film isolant a constante dielectrique elevee, element capacitif a film mince, condensateur lamine a films minces et procede de fabrication d'element capacitif a film mince WO2004065669A1 (fr)

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US10/542,847 US20060279901A1 (en) 2003-01-21 2004-01-16 Thin film capacitance element composition, high permittivity insulation film, thin film capacitance element, thin film multilayer capacitor and production method of thin film capacitance element
EP04702806A EP1591567A1 (fr) 2003-01-21 2004-01-16 Composition pour element capacitif a film mince, film isolant a constante dielectrique elevee, element capacitif a film mince, condensateur lamine a films minces et procede de fabrication d'element capacitif a film mince
JP2005508042A JP4529902B2 (ja) 2003-01-21 2004-01-16 薄膜容量素子用組成物、高誘電率絶縁膜、薄膜容量素子、薄膜積層コンデンサおよび薄膜容量素子の製造方法

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GB2417243A (en) * 2004-08-18 2006-02-22 Nat Inst Of Advanced Ind Scien Complex oxide having p-type thermoelectric characteristics
JP2007150186A (ja) * 2005-11-30 2007-06-14 Tdk Corp 薄膜電子部品用電極、薄膜電子部品及びその製造方法
US7580241B2 (en) 2004-04-26 2009-08-25 Tdk Corporation Thin film capacitor element composition, high permittivity insulation film, thin film capacitor element, thin film multilayer capacitor, and method of production of thin film capacitor element
JP5590224B2 (ja) * 2011-03-25 2014-09-17 株式会社村田製作所 積層セラミックコンデンサおよびその製造方法
WO2017057423A1 (fr) * 2015-10-02 2017-04-06 株式会社村田製作所 Dispositif lc de type monté en surface

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Publication number Priority date Publication date Assignee Title
US8871111B2 (en) * 2008-03-18 2014-10-28 Ngk Insulators, Ltd. Piezoelectric/electrostrictive ceramic composition
CN101607818B (zh) * 2009-07-06 2012-05-23 扬州大学 具有多铁性能的层状结构钛铁钴酸铋陶瓷材料及其制备方法
CN101792312A (zh) * 2010-03-10 2010-08-04 天津大学 SrTiO3陶瓷电介质材料及其电容器的制备方法
KR101728255B1 (ko) * 2012-08-27 2017-04-18 캐논 가부시끼가이샤 압전 재료, 그것을 사용한 압전 소자 및 그 압전 소자를 사용한 전자 기기
CN109796205B (zh) * 2019-02-20 2021-12-28 山东大学 一种铋层状结构钛钽酸铋高温压电陶瓷材料及其制备方法
CN114349498A (zh) * 2022-01-21 2022-04-15 福建工程学院 一种BNT-BiGaO3基铁电陶瓷材料及其制备方法和应用
CN117303890A (zh) * 2023-09-08 2023-12-29 中山大学 一种铋层状压电陶瓷材料及其制备方法和应用

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10148087A (ja) * 1996-11-20 1998-06-02 Morimotogumi:Kk 立坑構築における坑内土砂の排出方法及びその装置
EP0877100A1 (fr) * 1997-05-06 1998-11-11 Sharp Kabushiki Kaisha Procédé de fabrication de solutions solides de matériaux de perovskite en couches
US20020153543A1 (en) * 1998-09-29 2002-10-24 Takeshi Kijima Method for manufacturing oxide ferroelectric thin film oxide ferroelectric thin film and oxide ferroelectric thin film element

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030152813A1 (en) * 1992-10-23 2003-08-14 Symetrix Corporation Lanthanide series layered superlattice materials for integrated circuit appalications
JP2000169297A (ja) * 1998-09-29 2000-06-20 Sharp Corp 酸化物強誘電体薄膜の製造方法、酸化物強誘電体薄膜及び酸化物強誘電体薄膜素子
JP2002025856A (ja) * 2000-07-06 2002-01-25 Nec Corp 積層コンデンサ及び半導体装置並びに電子回路基板

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10148087A (ja) * 1996-11-20 1998-06-02 Morimotogumi:Kk 立坑構築における坑内土砂の排出方法及びその装置
EP0877100A1 (fr) * 1997-05-06 1998-11-11 Sharp Kabushiki Kaisha Procédé de fabrication de solutions solides de matériaux de perovskite en couches
US20020153543A1 (en) * 1998-09-29 2002-10-24 Takeshi Kijima Method for manufacturing oxide ferroelectric thin film oxide ferroelectric thin film and oxide ferroelectric thin film element

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7580241B2 (en) 2004-04-26 2009-08-25 Tdk Corporation Thin film capacitor element composition, high permittivity insulation film, thin film capacitor element, thin film multilayer capacitor, and method of production of thin film capacitor element
GB2417243A (en) * 2004-08-18 2006-02-22 Nat Inst Of Advanced Ind Scien Complex oxide having p-type thermoelectric characteristics
GB2417243B (en) * 2004-08-18 2006-12-13 Nat Inst Of Advanced Ind Scien Complex oxide having p-Type thermoelectric characteristics
US7554029B2 (en) 2004-08-18 2009-06-30 National Institute Of Advanced Industrial Science And Technology Complex oxide having p-type thermoelectric characteristics
JP2007150186A (ja) * 2005-11-30 2007-06-14 Tdk Corp 薄膜電子部品用電極、薄膜電子部品及びその製造方法
JP5590224B2 (ja) * 2011-03-25 2014-09-17 株式会社村田製作所 積層セラミックコンデンサおよびその製造方法
WO2017057423A1 (fr) * 2015-10-02 2017-04-06 株式会社村田製作所 Dispositif lc de type monté en surface
JP6288386B2 (ja) * 2015-10-02 2018-03-07 株式会社村田製作所 表面実装型ｌｃデバイス
JPWO2017057423A1 (ja) * 2015-10-02 2018-03-29 株式会社村田製作所 表面実装型ｌｃデバイス
US10950381B2 (en) 2015-10-02 2021-03-16 Murata Manufacturing Co., Ltd. Surface-mounted LC device

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EP1591567A1 (fr) 2005-11-02
TW200503018A (en) 2005-01-16
CN1742121A (zh) 2006-03-01
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